CN110523423A - A kind of preparation and application of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst - Google Patents
A kind of preparation and application of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst Download PDFInfo
- Publication number
- CN110523423A CN110523423A CN201910636234.8A CN201910636234A CN110523423A CN 110523423 A CN110523423 A CN 110523423A CN 201910636234 A CN201910636234 A CN 201910636234A CN 110523423 A CN110523423 A CN 110523423A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- preparation
- phosphorus oxygen
- dioxide photocatalyst
- oxygen doping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000013067 intermediate product Substances 0.000 claims abstract description 14
- 229960000789 guanidine hydrochloride Drugs 0.000 claims abstract description 11
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 claims description 21
- 229960000740 enrofloxacin Drugs 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000003115 biocidal effect Effects 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 230000005291 magnetic effect Effects 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 229940088710 antibiotic agent Drugs 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- 229960004198 guanidine Drugs 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000008236 heating water Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000007146 photocatalysis Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001055 reflectance spectroscopy Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012984 antibiotic solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to catalysis material technical fields, and in particular to a kind of preparation and application of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst.The present invention provides a kind of preparation methods of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst, comprising the following steps: step 1: guanidine hydrochloride, hexachlorocyclotriph,sphazene, polyvinylpyrrolidone and anatase titania being mixed, heating water bath is evaporated to obtain intermediate product powder；Step 2: intermediate product powder progress heat polymerization is obtained into composite photo-catalyst.The present invention also provides the composite photo-catalyst prepared by the above method and its applications.The preparation and application of phosphorus oxygen provided by the invention doping carbonitride composite titanium dioxide photocatalyst, solve that existing preparation process is cumbersome, and preparation time is long, are unfavorable for the technical issues of being industrially mass produced.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of phosphorus oxygen doping carbonitride composite titanium dioxide light
The preparation and application of catalyst.
Background technique
Enrofloxacin antibiotic is widely used in the bacterium infection for the treatment of humans and animals in the world.Due to its chemistry knot
Structure is stablized, and is not easy to be biodegradable, Enrofloxacin antibiotic can not be effectively removed by traditional sewage treatment process.Although grace promise
The concentration of husky star antibiotic in the natural environment is very low, but since it has false duration phenomenon, long-term accumulation, is led in the environment
The generation for causing drug-resistant bacteria, to cause damages to aquatile and human health.At present in water body antibiotic minimizing technology
Mainly there are physical method, chemical method and bioanalysis, existing biotechnology and chemical oxidation method are time-consuming, low efficiency, are also easy to produce two
Secondary pollution.Wherein Photocatalyst is the energy using sunlight, has high treatment efficiency, low cost, green non-pollution etc.
Advantage, it is widely used by people.
In recent years, carbonitride (CN) be used as a kind of nonmetallic high-molecular optical catalyst, due to its good chemical stability,
Thermal stability, hypotoxicity, bio-compatibility and have it is visible light-responded, have been widely used for photocatalysis degradation organic contaminant
Field.However, single carbonitride photogenerated carriers recombination fraction is high, it is seen that light utilization efficiency is low, and specific surface area is small, seriously limits it
Photocatalysis performance.Therefore scientific research personnel uses a variety of methods to improve the performance of carbonitride, wherein nonmetal doping and
Compound with semiconductor material is two kinds of economically viable methods.
Nonmetal doping is the effective ways for adjusting carbonitride unique electronic structure and band gap, it is widened significantly
Optical response range enhances separation of charge and improves specific surface area, while improving carbonitride photocatalysis performance, keeps nitrogen
Change carbon without metallicity.Carbonitride and semiconductor material are compounded to form hetero-junctions, can inhibit the recombination fraction of photogenerated carriers, from
And improve the photocatalysis performance of carbonitride.
Existing preparation process is cumbersome, and preparation time is long, needs high-temperature high-pressure apparatus more, and raw material is more, is unfavorable for industrial big
The defect of large-scale production becomes those skilled in the art's technical problem urgently to be resolved.
Summary of the invention
The present invention provides the preparations and application of a kind of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst, solve
Existing preparation process is cumbersome, and preparation time is long, is unfavorable for the technical issues of being industrially mass produced.
The purpose of the present invention is realized by following technical proposals:
A kind of preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst, comprises the following specific steps that:
Step 1: by guanidine hydrochloride, it is super that 20mL is added in hexachlorocyclotriph,sphazene, polyvinylpyrrolidone and anatase titania
Pure water, after completely dissolution, under the conditions of magnetic agitation, water bath method obtains intermediate product to ultrasound；
Step 2: intermediate product being milled, calcines in Muffle furnace, after it is cooled to room temperature, mills, is sieved, it is multiple to obtain P
Light combination catalyst.
Preferably, guanidine hydrochloride described in step 1, hexachlorocyclotriph,sphazene, polyvinylpyrrolidone and anatase titania
Quality be guanidine hydrochloride: 2~5g, hexachlorocyclotriph,sphazene: 0.3~0.75g, polyvinylpyrrolidone: 0.2~0.5mg, anatase
Titanium dioxide: 2~10g.
Preferably, bath temperature described in step 1 is 60~80 DEG C.
Preferably, calcination temperature is 500~550 DEG C in Muffle furnace described in step 2.
Preferably, calcination time is 3~4h in Muffle furnace described in step 2.
Preferably, the heating rate of calcining described in step 2 is 2~3 DEG C/min.
Preferably, the screen-aperture of sieving described in step 2 is 100 mesh.
A kind of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst is prepared by the above method.
Application of the phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst in degradation field of antibiotics.
Preferably, the antibiotic is Enrofloxacin.
Above-mentioned phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst is degraded Enrofloxacin antibiosis under simulated solar irradiation
The method of application in element is specific as follows: weighing catalyst described in 0.05g and is placed in quartzy photodissociation pipe, it is dense that 50ml is added thereto
Degree is the Enrofloxacin antibiotic solution of 10mg/l.Using 300W xenon lamp configuration 420nm optical filter be light source, illumination 60~
The amount of remaining Enrofloxacin antibiotic in liquid chromatogram measurement solution is used after 80min.
Compared with prior art, the invention has the following advantages:
1. the phosphorus oxygen that the present invention is prepared adulterates carbonitride composite titanium dioxide photocatalyst, phosphorus atoms are introduced, are replaced
The carbon atom of graphite phase carbon nitride frame mid portion point, reduces the recombination rate of electronics and hole in catalytic process, and enhances visible light
It absorbs, to improve photocatalysis efficiency.Oxygen atom is introduced, the nitrogen-atoms of graphite phase carbon nitride frame mid portion point is replaced, improves light
The specific surface area of catalyst, to improve photocatalysis efficiency.
2. introducing anatase titania conduct in phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst of the invention
Composite object can inhibit the compound of electronics and hole in catalytic process, to improve photocatalysis effect by forming binary hetero-junctions
Rate.
3. preparation method provided by the invention is simple thermal polymerization, preparation method repeatability and controllability are good, material
Stability is good, can meet volume production requirement well, there is higher application prospect and use value.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is the SEM comparison diagram of the embodiment of the present invention 1, comparative example 1 and comparative example 2；
Fig. 2 is that the TEM of the embodiment of the present invention 1 schemes；
Fig. 3 is comparative example 1 of the present invention, the x-ray photoelectron comparison energy spectrum diagram of comparative example 2；
Fig. 4 is the comparison UV Diffuse Reflectance Spectroscopy of the embodiment of the present invention 1, comparative example 1 and comparative example 2；
Fig. 5 is that the electron paramagnetic resonance of the embodiment of the present invention 1, comparative example 2 compares map；
Fig. 6 is the embodiment of the present invention 1, comparative example 1 and comparative example 2 respectively to Enrofloxacin removal efficiency comparison diagram；
Fig. 7 is the degradation rate figure of the embodiment of the present invention 1 three times to Enrofloxacin circulation.
Specific embodiment
The present invention provides the preparations and application of a kind of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst, solve
Existing preparation process is cumbersome, and preparation time is long, is unfavorable for the technical issues of being industrially mass produced.
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, the embodiment described is the embodiment of part of representative of the invention, rather than whole embodiments, this field are general
Other all embodiments obtained belong to protection of the invention to logical technical staff without making creative work
Range.
Raw material employed in the embodiment of the present invention and instrument are commercially available；Wherein photochemical reactor is XPA-7, lamp source
For 300W xenon lamp and it is configured with 420nm optical filter, is purchased from Xujiang Electromechanical Plant, Nanjing, China.
Embodiment 1
A kind of preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst, comprising the following steps:
1. weighing 2.5g guanidine hydrochloride, 0.375g hexachlorocyclotriph,sphazene, 0.25mg polyvinylpyrrolidone and 2.5g anatase
Titanium dioxide is placed in alumina crucible, thereto be added 20ml ultrapure water, ultrasound after completely dissolution, in the condition of magnetic agitation
Under, 70 DEG C of water bath methods mill to obtain intermediate product after water evaporating completely.
2. the crucible equipped with intermediate product powder is transferred to Muffle furnace, 550 DEG C are risen to 2 DEG C/min heating rate and is protected
Hold temperature calcination 4h.It after being cooled to room temperature, is sufficiently milled with agate mortar, the sieve through 100 mesh obtains phosphorus oxygen doping
Carbonitride composite titanium dioxide photocatalyst, that is, POCN/TiO2Composite photo-catalyst.
Embodiment 2
A kind of preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst, comprising the following steps:
1. weighing 3g guanidine hydrochloride, 0.375g hexachlorocyclotriph,sphazene, 0.35mg polyvinylpyrrolidone and 5g anatase dioxy
Change titanium be placed in alumina crucible, thereto be added 20ml ultrapure water, ultrasound after completely dissolution, under conditions of magnetic agitation,
60 DEG C of water bath methods mill to obtain intermediate product after water evaporating completely.
2. the crucible equipped with intermediate product powder is transferred to Muffle furnace, 520 DEG C are risen to 2 DEG C/min heating rate and is protected
Hold temperature calcination 4h.It after being cooled to room temperature, is sufficiently milled with agate mortar, the sieve through 100 mesh obtains POCN/
TiO2Composite photo-catalyst.
Embodiment 3
A kind of preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst, comprising the following steps:
1. weighing 4g guanidine hydrochloride, 0.6g hexachlorocyclotriph,sphazene, 0.4mg polyvinylpyrrolidone and 8g anatase titania
Be placed in alumina crucible, thereto be added 20ml ultrapure water, ultrasound after completely dissolution, under conditions of magnetic agitation, 80 DEG C
Water bath method mills to obtain intermediate product after water evaporating completely.
2. the crucible equipped with intermediate product powder is transferred to Muffle furnace, 540 DEG C are risen to simultaneously with 2.5 DEG C/min heating rate
Keep temperature calcination 3.5h.It after being cooled to room temperature, is sufficiently milled with agate mortar, the sieve through 100 mesh obtains
POCN/TiO2Composite photo-catalyst.
Comparative example 1
A kind of preparation of carbonitride (CN) photochemical catalyst, comprising the following steps:
It weighs 2.5g guanidine hydrochloride to be placed in alumina crucible, transfer them in Muffle furnace with 2 DEG C/min heating rate liter
To 550 DEG C and the temperature is kept to carry out reaction 4h.After it is cooled to room temperature, sufficiently milled with agate mortar, the sieve through 100 mesh
Son sieving, obtains CN photochemical catalyst.
Comparative example 2
A kind of preparation of phosphorus oxygen codope carbonitride (POCN) photochemical catalyst, comprising the following steps:
1. weighing 2.5g guanidine hydrochloride, 0.375g hexachlorocyclotriph,sphazene and 0.25mg polyvinylpyrrolidone is placed in aluminium oxide earthenware
In crucible, thereto be added 20ml ultrapure water, ultrasound after completely dissolution, under conditions of magnetic agitation, 70 DEG C of water bath methods, to water
After evaporating completely, mill to obtain intermediate product.
2. the crucible equipped with intermediate product powder is transferred to Muffle furnace, 550 DEG C are risen to 2 DEG C/min heating rate and is protected
Hold temperature calcination 4h.It after being cooled to room temperature, is sufficiently milled with agate mortar, the sieve through 100 mesh obtains POCN light and urges
Agent.
To sum up, to the TiO prepared in embodiment 12And POCN/TiO2, POCN points in CN and comparative example 2 in comparative example 1
Not carry out sem analysis, as a result as shown in Figure 1.Wherein (a) is CN, (b) is POCN, (c) is TiO2, (d) be POCN/TiO2, by
Fig. 1 is it is found that POCN and CN have class graphene-structured, in bulk, no significant difference, the POCN/ that will be prepared in embodiment 1
TiO2Tem analysis is carried out respectively, as shown in Figure 2.As shown in Figure 2, TiO2Crystal is attached on the CN of sheet, shows the composite wood
Expect successfully to prepare.
By Fig. 3 a it is found that phosphorus atoms be successfully doped to nitridation carbon structure in, instead of carbon atom and with adjacent nitrogen-atoms
Form P-N.By Fig. 3 d it is found that oxygen atom is successfully doped in nitridation carbon structure, instead of nitrogen-atoms and C-O-C is formd.
Fig. 3 b and c show that the doping of phosphorus and oxygen does not have an impact the overall structure of carbonitride.Fig. 4 is the TiO in embodiment 12With
POCN/TiO2, the CN in comparative example 1, the POCN in comparative example 2 UV Diffuse Reflectance Spectroscopy spectrogram.As seen from Figure 4, pure TiO2
Sample shows stronger light absorpting ability and absorption edge at 390nm.In addition, with pure TiO2It compares, POCN/TiO2Sample
Light absorpting ability at 400-500nm increases.This illustrates that compound POCN enhances TiO2Visible light absorption capacity.
Fig. 5 is the TiO in embodiment 12And POCN/TiO2, POCN in comparative example 2 electron paramagnetic resonance spectrum figure.By scheming
5 it is found that comparison TiO2And POCN, POCN/TiO2Superoxide radical (O2 ·-), hydroxyl radical free radical (OH) and singlet oxygen
(1O2) three kinds of Free Radical Signal intensity are higher than other two kinds of materials, POCN/TiO2The free base unit weight that photoreactivation catalyst generates
At most, show POCN/TiO2Photocatalysis performance it is more preferable.
The embodiment of the invention also provides a kind of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalysts in Enrofloxacin
Application in antibiotic waste water processing, comprising the following steps:
(1) the Enrofloxacin solution that configuration 50ml concentration is 10mg/L, is added POCN/TiO made from 50mg embodiment 12
Composite photo-catalyst, ultrasonic 10min, which is placed in photochemical reactor, is protected from light absorption 30min.
(2) this application is using 300W xenon lamp configuration 420nm optical filter as light-catalyzed reaction light source, and solution is in illumination
60min takes out and uses the concentration C of liquid chromatogram measuring solution residue Enrofloxacin.According to formula P=(C0- C) * 100% meter
The removal rate of Enrofloxacin is calculated, wherein C0For the initial concentration of Enrofloxacin.As a result as shown in Figure 6.
(3) CN obtained in 50mg comparative example 1 is weighed, is repeated step (1) (2), obtains catalyst CN to Enrofloxacin
Removal rate, as a result as shown in Figure 6.
(4) POCN obtained in 50mg comparative example 2 is weighed, is repeated step (1) (2), obtains catalyst POCN to En Nuosha
The removal rate of star, as a result as shown in Figure 6.
It can be obtained by Fig. 6, under simulated solar irradiation after photodissociation 60min, the POCN/TiO that is prepared in embodiment 12Complex light
Catalyst is 92.7% to the removal rate of Enrofloxacin, all higher than CN (32.2%) and POCN (75.6%), illustrates that phosphorus oxygen is double-doped
Miscellaneous and and TiO2Recombination energy significantly improve the catalytic performance of carbon nitride catalyst.
The POCN/TiO that will be reacted in Enrofloxacin antibiotic waste water2Composite photo-catalyst is filtered, and using ultrapure
Twice of washing, dehydrated alcohol is washed one time, be placed in 60 DEG C of baking ovens and be dried overnight.POCN/ after weighing 50mg reacting drying
TiO2Composite photo-catalyst repeats the step of Enrofloxacin antibiotic waste water is handled (1) (2), POCN/ after calculating circulation twice
TiO2Removal rate of the composite photo-catalyst to Enrofloxacin.It repeats test to carry out 3 times altogether, detects composite wood after 3 cyclic tests
Expect the removal rate to Enrofloxacin, as a result as shown in Figure 7.As shown in Figure 7, in the 3rd cyclic test, POCN/TiO2It is compound
Photochemical catalyst still can reach 90.5% to the removal rate of Enrofloxacin, illustrate POCN/TiO prepared by the present invention2Composite photocatalyst
Agent has good photocatalysis stability.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention that claims determine, also
Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by
The range of claims determines.
Claims (10)
1. a kind of preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst, which is characterized in that including having as follows
Body step:
Step 1: by guanidine hydrochloride, 20mL ultrapure water is added in hexachlorocyclotriph,sphazene, polyvinylpyrrolidone and anatase titania,
After completely dissolution, under the conditions of magnetic agitation, water bath method obtains intermediate product to ultrasound；
Step 2: intermediate product being milled, calcines in Muffle furnace, after it is cooled to room temperature, mills, is sieved, is obtained complex light and urge
Agent.
2. the preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst according to claim 1, feature
It is, guanidine hydrochloride described in step 1, the quality of hexachlorocyclotriph,sphazene, polyvinylpyrrolidone and anatase titania is salt
Sour guanidine: 2~5g, hexachlorocyclotriph,sphazene: 0.3~0.75g, polyvinylpyrrolidone: 0.2~0.5mg, anatase titania: 2
~10g.
3. the preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst according to claim 1, feature
It is, bath temperature described in step 1 is 60~80 DEG C.
4. the preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst according to claim 1, feature
It is, calcination temperature is 500~550 DEG C in Muffle furnace described in step 2.
5. the preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst according to claim 1, feature
It is, the time of calcining described in step 2 is 3~4h.
6. the preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst according to claim 1, feature
It is, the heating rate of calcining described in step 2 is 2~3 DEG C/min.
7. the preparation method of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst according to claim 1, feature
It is, the screen-aperture of sieving described in step 2 is 100 mesh.
8. a kind of phosphorus oxygen adulterates carbonitride composite titanium dioxide photocatalyst, which is characterized in that the phosphorus oxygen doping carbonitride is multiple
Titanium dioxide optical catalyst is closed to be prepared by the described in any item preparation methods of claim 1-7.
9. phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst as claimed in claim 8 is in degradation field of antibiotics
Using.
10. phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst according to claim 9 is in degradation field of antibiotics
In application, which is characterized in that the antibiotic be Enrofloxacin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910636234.8A CN110523423A (en) | 2019-07-15 | 2019-07-15 | A kind of preparation and application of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910636234.8A CN110523423A (en) | 2019-07-15 | 2019-07-15 | A kind of preparation and application of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110523423A true CN110523423A (en) | 2019-12-03 |
Family
ID=68660296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910636234.8A Pending CN110523423A (en) | 2019-07-15 | 2019-07-15 | A kind of preparation and application of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110523423A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437865A (en) * | 2020-04-28 | 2020-07-24 | 广东工业大学 | Composite photocatalyst and preparation method and application thereof |
| CN111547770A (en) * | 2020-06-05 | 2020-08-18 | 中国科学技术大学 | Preparation method of functionalized modified molybdenum disulfide nanosheet |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238083A (en) * | 2016-07-08 | 2016-12-21 | 东华大学 | A kind of preparation method of graphite phase carbon nitride/composite titania material catalyst |
-
2019
- 2019-07-15 CN CN201910636234.8A patent/CN110523423A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238083A (en) * | 2016-07-08 | 2016-12-21 | 东华大学 | A kind of preparation method of graphite phase carbon nitride/composite titania material catalyst |
Non-Patent Citations (7)
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437865A (en) * | 2020-04-28 | 2020-07-24 | 广东工业大学 | Composite photocatalyst and preparation method and application thereof |
| CN111547770A (en) * | 2020-06-05 | 2020-08-18 | 中国科学技术大学 | Preparation method of functionalized modified molybdenum disulfide nanosheet |
| CN111547770B (en) * | 2020-06-05 | 2021-05-07 | 中国科学技术大学 | Preparation method of functionalized modified molybdenum disulfide nanosheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20220355284A1 (en) | Perylene imide and composite photocatalytic material thereof, preparation method therefor and application thereof in removing organic pollutants from water | |
| Zhang et al. | Preparation and performances of mesoporous TiO2 film photocatalyst supported on stainless steel | |
| CN111921550B (en) | MXene/titanium dioxide nanotube composite photocatalyst and preparation method thereof | |
| CN105749893A (en) | Preparation method of modified active carbon fiber with surface-loaded nanometer titanium dioxide (TiO2) | |
| CN110756215B (en) | CoP-HCCN composite photocatalyst and preparation method and application thereof | |
| CN108160042B (en) | Utilize the method for ZnO thin film metal-organic framework materials processing antibiotic waste water | |
| CN110694662B (en) | Two-dimensional I-doped BiOIO 3 /g-C 3 N 4 Composite catalyst and preparation method and application thereof | |
| CN106861742A (en) | A kind of zinc oxide nano rod/g C3N4The preparation method of nanometer sheet composite photocatalyst material | |
| CN111185215B (en) | Carbon dot modified carbon nitride/tin dioxide composite photocatalyst and preparation method and application thereof | |
| CN110523423A (en) | A kind of preparation and application of phosphorus oxygen doping carbonitride composite titanium dioxide photocatalyst | |
| CN108325555A (en) | Nitrogen auto-dope is graphitized azotized carbon nano piece photochemical catalyst and its preparation method and application | |
| CN107715861A (en) | Culm biology carbon quantum dot modifies Bi4Ti3O12The preparation and its application of composite photo-catalyst | |
| CN108686692A (en) | A kind of photochemical catalyst and its preparation method and application of oxygen doping carbonitride | |
| CN108654586A (en) | A kind of graphitization mesoporous carbon-TiO2Composite photocatalyst material and the preparation method and application thereof | |
| CN109603809A (en) | A kind of preparation and application of pucherite quantum dot and titanium dioxide nano-belts composite photo-catalyst | |
| CN109647371A (en) | A kind of heterojunction composite photocatalyst and its preparation method and application | |
| CN105344343B (en) | A kind of preparation method of visible light-responded carbon-doped nano titanium deoxid catalyst | |
| CN104841463A (en) | BiOCl/P25 composite photocatalyst, and preparation method and applications thereof | |
| CN111001400B (en) | Titanium dioxide material and preparation method thereof | |
| CN111632619A (en) | Copper-nitrogen co-doped titanium dioxide photocatalytic material, preparation method and application | |
| CN110373891A (en) | Load bismuth tungstate/visible light-responded composite antibacterial fabric of titanium dioxide/redox graphene and preparation method thereof | |
| CN107684914A (en) | A kind of magnetic Bi2MoO6/CuFe2O4Composite photocatalyst material and preparation method thereof | |
| CN115779946A (en) | Boron-nitrogen co-doped titanium dioxide nanotube composite material and preparation method thereof | |
| CN107308960A (en) | A kind of niobic acid tellurium catalysis material and its preparation method and application | |
| Yuhaneka et al. | Synthesis of Porous g-C₃N₄ and Its Application as Photocatalyst for Methylene Blue Degradation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191203 |